Structural and antireflective properties of ZnO nanorods synthesized using the sputtered ZnO seed layer for solar cell applications

We report the structural and antireflective properties of ZnO nanorod arrays (NRAs) on silicon (Si) substrate by wet chemical growth using the sputtered ZnO seed layer for solar cell applications. The size, height, shape, and number of ZnO nanorods depend strongly on the ZnO seed layer thickness as well as the molar zinc nitrate concentration. Clearly, the ZnO nanorods are of wurzite crystal structure from the X-ray diffraction analysis. To achieve the low reflectance over a wide wavelength range, the ZnO seed layer thickness, molar concentration, and growth time are optimized. It is found that the specular reflection spectrum of ZnO NRAs is closely related to the ZnO seed layer thickness. The solar weighted reflectance, Rw, of ZnO NRAs as antireflection coatings for Si solar cells is estimated under AM1.5 g illumination. For ZnO NRAs with 50 nm ZnO seed layer in 10 mM aqueous solution for 12 hours, the low specular reflectance (i.e., <7%) is obtained at wavelengths of 300-1200 nm, indicating a low Rw of 3.86%.     

Er-doped ZnO nanorod arrays with enhanced 1540 nm emission by employing Ag island films and high-temperature annealing

Single-crystalline Er-doped ZnO nanorod arrays (NRAs) on Ag island films with appropriate annealing show a promising enhancement of 1540 nm emission for optical communication. The enhanced 1540 nm emission of Er-doped ZnO NRAs is attributed to the enhancement of the deep level emission of ZnO host. In an effort to enhance deep level emission to pump Er(3+) emission at 1540 nm in the Er-doped ZnO NRAs, surface plasmon coupling and increase in deep level states were carried out via Ag island films and high-temperature annealing. This study points to the effective methods to enhance 1540 nm emission, demonstrating that ZnO NRAs with Ag islands have a promising potential for the application in optical communications.     

Combination of surface texturing and nanostructure coating for reduction of light reflection in ZnO/Si heterojunction thin film solar cell

In this study, we report a single heterojunction solar cell based on n-type zinc oxide/p-type silicon. Three different solar cells were fabricated based on ZnO thin film on Si substrate, ZnO nanorods on Si substrate, and ZnO nanorods on micro-pyramidal structure of Si substrate. The comparison between these three kinds of solar cells was studied. Pyramidal structure of silicon was fabricated using chemical etching technique of p-type Si (100). The chemical solution consists of NaOH, isopropyl alcohol and hydrazine hydrate. The results showed that Si micro-pyramids can enhance optical absorption of Si substrates by increasing surface area and entrapping of incident light. For fabrication of uniform ZnO nanorods, a seed layer of ZnO was deposited on Si substrates via radio frequency magnetron sputtering technique. This layer can be used as an active n-type material in heterojunction solar cells as well. ZnO nanostructures can increase light absorption due to their high specific surface area. The combination of ZnO nanorods and Si micro-pyramids can enhance light trapping effect and increase the efficiency of solar cells. The structural and morphology of samples were studied using field-emission scanning electron microscopy, atomic force microscopy and X-ray diffractometry while the optical properties were investigated using photoluminescence and reflectance spectrometry. The efficiency and fill factor of solar cells were obtained from current–voltage characteristics using a solar simulator and a source-meter. The results showed that the efficiency of solar cell based on nanostructures of ZnO/micropyramids of Si is highly increased due to high anti-reflective behavior of this sample.     

Broadband and wide-angle antireflection subwavelength structures of Si by inductively coupled plasma etching using dewetted nanopatterns of Au thin films as masks

We report the broadband and wide-angle antireflection subwavelength structures (SWSs) on silicon (Si) substrate by inductively coupled plasma (ICP) etching using gold (Au) nanopatterns as etch masks. The reflectance depends strongly on the etched profile of Si SWSs which is influenced by both thermal dewetting and etching conditions. The size, shape, and array geometry of nano-sized patterns, which are produced via the thermal dewetting of Au thin films, are optimized under proper heat treatment. The etched depth and shape of Si nano tips are controlled additionally by ICP power, thus achieving the efficient antireflection characteristics. The optimized Si SWS with the tapered structure and sharp tips at high ICP power leads to a significantly low reflectance value of < 1% at wavelengths of 350-1100 nm. Furthermore, it exhibits a wide-angle antireflection property of < 7.5% at incident angles of 8-70° over a wide wavelength range of 300-1100 nm.     

Pyramidal nanostructures of zinc oxide

Zinc oxide (ZnO) nanostructures have been prepared by pulsed laser deposition of the oxide onto Si(100) substrate at 600 degrees C. An examination of the morphology using atomic force microscopy and scanning electron microscopy reveals well formed pyramidal structures consistent with the growth habit of ZnO. A domain matched epitaxy across the interface makes the ZnO pyramids orient along the axes of Si(100) surface. The pyramidal nanostructures signify an intermediate state in the growth of hexagonal nanorods of ZnO. The hardness of the nanostructures as well as their response to oxygen gas have been investigated using nanoindentation and conducting probe methods respectively. ZnO nanostructures are much harder than their bulk. The hardness of ZnO pyramids obtained by nanoindentation is 70 +/- 10 GPa which is about one order more that of bulk ZnO. Besides, the nanostructures exhibit high sensitivity towards oxygen. A 70% increase in the resistance of ZnO nanostructures is observed when exposed to oxygen atmosphere.     

Effect of AZO seed layer on electrochemical growth and optical properties of ZnO nanorod arrays on ITO glass

We report the structural and optical properties of ZnO nanorod arrays (NRAs) grown by an electrochemical deposition process. The ZnO NRAs were grown on indium tin oxide (ITO) coated glass substrates with a thin sputtered Al-doped ZnO (AZO) seed layer and compared with ones directly grown without the seed layer. The growth condition dependence of ZnO NRAs was investigated for various synthetic parameters. The morphology and density of the ZnO NRAs were accordingly controlled by means of zinc nitrate concentration and growth time. From photoluminescence results, the ultraviolet emission was significantly enhanced after thermal treatment. For ZnO NRAs grown on ITO glass without the seed layer, the diffuse transmittance was enhanced despite the reduction in the total transmittance, indicating a high haze value. By using a thin AZO seed layer, the well-aligned ZnO NRAs on AZO/ITO glass are controllably and reproducibly synthesized by varying the growth parameters, exhibiting a total transmittance higher than 91% in the visible wavelength range as well as good optical and crystal quality.     

Silver nanoisland induced synthesis of ZnO nanostructures by vapor phase transport

ZnO nanostructures including nanorod and nanotower were synthesized on Ag nanoisland coated Si substrate by thermal evaporation and vapor phase transport at atmospheric pressure. The as-prepared ZnO nanorods and nanotowers were single crystal growing along [0001] direction. The growth of ZnO nanostructures strongly depended on the surface morphology of the nanoisland Ag film deposited by electroless nanoelectrochemistry. The growth mechanism of the ZnO nanostructures was proposed on the basis of experimental data. A strong room-temperature photoluminescence in ZnO nanostructures has been demonstrated. The growth technique would be of particular interest for direct integration in the current silicon-technology-based optoelectronic devices.     

Immobilization of angiotensin II and bovine serum albumin on strip-patterned ZnO nanorod arrays

For an effective protein immobilization for highly sensitive biosensors, we determined the binding properties and characteristics of angiotensin II and bovine serum albumin on the surface of patterned ZnO nanorod arrays (NRAs) which were selectively grown on desired areas of Si substrates. The surfaces of ZnO NRAs were modified by 3-aminopropyltriethoxysilane and gluteraldehyde, and the activated NRAs were then conjugated with angiotensin II protein and bovine serum albumin. The silanization process and conjugation of protein were verified by secondary ion mass spectroscopy (SIMS) and X-ray photoelectron spectroscopy (XPS) techniques. The immobilizing densities of proteins determined by Coomassie protein assay were 4.5 microg/cm2 for angiotensin II and 5.3 microg/cm2 for bovine serum albumin.     

Microstructure and optical properties of Ag-doped ZnO nanostructures prepared by a wet oxidation doping process

Silver-doped zinc oxide (Ag:ZnO) nanostructures were prepared by a facile and efficient wet oxidation method. This method included two steps: metallic Zn thin films mixed with Ag atoms were prepared by magnetron sputtering as the precursors, and then the precursors were oxidized in an O(2) atmosphere with water vapour present to form Ag:ZnO nanostructures. By controlling the oxidation conditions, pure ZnO and Ag:ZnO nanobelts/nanowires with a thickness of ～ 20 nm and length of up to several tens of microns were synthesized. Scanning electron microscopy, transmission electron microscopy, cathodoluminescence and low temperature photoluminescence (PL) measurements were adopted to characterize the microstructure and optical properties of the prepared samples. The results indicated that Ag doping during magnetron sputtering was a feasible method to tune the optical properties of ZnO nanostructures. For the Ag:ZnO nanostructures, the intensity of ultraviolet emission was increased up to three times compared with the pure ones. The detailed PL intensity variation with the increasing temperature is also discussed based on the ionization energy of acceptor in ZnO induced by Ag dopants.     

Plasmonic ZnO/Ag Embedded Structures as Collecting Layers for Photogenerating Electrons in Solar Hydrogen Generation Photoelectrodes

A new fabrication strategy in which Ag plasmonics are embedded in the interface between ZnO nanorods and a conducting substrate is experimentally demonstrated using a femtosecond‐laser (fs‐laser)‐induced plasmonic ZnO/Ag photoelectrodes. This fs‐laser fabrication technique can be applied to generate patternable plasmonic nanostructures for improving their effectiveness in hydrogen generation. Plasmonic ZnO/Ag nanostructure photoelectrodes show an increase in the photocurrent of a ZnO nanorod photoelectrodes by higher than 85% at 0.5 V. Both localized surface plasmon resonance in metal nanoparticles and plasmon polaritons propagating at the metal/semiconductor interface are available for improving the capture of sunlight and collecting charge carriers. Furthermore, in‐situ X‐ray absorption spectroscopy is performed to monitor the plasmonic‐generating electromagnetic field upon the interface between ZnO/Ag nanostructures. This can reveal induced vacancies on the conduction band of ZnO, which allow effective separation of charge carriers and improves the efficiency of hydrogen generation. Plasmon‐induced effects enhance the photoresponse simultaneously, by improving optical absorbance and facilitating the separation of charge carriers.     

Size-dependent optical behavior of disordered nanostructures on glass substrates

We demonstrate the distinctive optical properties of disordered nanostructures on glass substrates in accordance with changes in the average size of the nanostructures. Dissimilar sizes of nanostructures were fabricated by using different thicknesses of thermally dewetted Ag nanoparticles as etch masks. Unlike a flat glass substrate, the nanostructured glasses (NSGs) show a changed optical characteristic. By increasing the size of the nanostructures, the wavelength of the peak transmittance of about 99% gradually moved from 730 to 2000?nm. To clearly discern the effect of the different sizes of nanostructures, the normalized angle-dependent transmittance spectra of the NSGs were analyzed. Only if the size becomes relatively larger than the wavelength of the incident light are the transmittance spectra more strongly affected by the incident angle as well as by the relative size, rather than by the Fresnel reflection.     

Fabrication and configuration development of silicon nitride sub-wavelength structures for solar cell application

To replace the double layer antireflection coating and improve the efficiency of solar cell, a self assembled nickel nano particle mask followed by inductively coupled plasma (ICP) ion etching method is proposed to form the sub-wavelength structures (SWS) on silicon nitride (Si3N4) antireflection coating layers instead of semiconductor layer. The size and density of nickel nano particles can be controlled by the initial thickness of nickel film that is annealed to form the nano-particles on the Si3N4 film deposited on the silicon substrate. ICP etching time is responsible for controlling the height of the fabricated Si3N4 SWS on silicon substrate, which is seen from our experiment. It is found that the lowest average reflectivity of 3.12% for wavelength ranging from 350 to 1000 nm is achieved when the diameter and height of the SWS are 120-180 nm and 150-160 nm, respectively. A low reflectance below 1% is observed over the wavelength from 590 to 680 nm for the fabricated Si3N4 SWS on silicon subs. The efficiency of Si3N4 SWS could be improved by 1.31%, compared with the single layer anti-reflection (SLAR) coatings of Si3N4, using PC1D program. The results of this study may benefit the fabrication of solar cells.     

ZnO nanostructures as efficient antireflection layers in solar cells

An efficient antireflection coating (ARC) can enhance solar cell performance through increased light coupling. Here, we investigate solution-grown ZnO nanostructures as ARCs for Si solar cells and compare them to conventional single layer ARCs. We find that nanoscale morphology, controlled through synthetic chemistry, has a great effect on the macroscopic ARC performance. Compared with a silicon nitride (SiN) single layer ARC, ZnO nanorod arrays display a broadband reflection suppression from 400 to 1200 nm. For a tapered nanorod array with average tip diameter of 10 nm, we achieve a weighted global reflectance of 6.6%, which is superior to an optimized SiN single layer ARC. Calculations using rigorous coupled wave analysis suggest that the tapered nanorod arrays behave like modified single layer ARCs, where the tapering leads to impedance matching between Si and air through a gradual reduction of the effective refractive index away from the surface, resulting in low reflection particularly at longer wavelengths and eliminating interference fringes through roughening of the air-ZnO interface. According to the calculations, we may further improve ARC performance by tailoring the thickness of the bottom fused ZnO layer and through better control of tip tapering.     

Bulk Micromachining of Si by Metal‐assisted Chemical Etching

Bulk micromachining of Si is demonstrated by the well‐known metal‐assisted chemical etching (MaCE). Si microstructures, having lateral dimension from 5 μm up to millimeters, are successfully sculpted deeply into Si substrate, as deep as >100 μm. The key ingredient of this success is found to be the optimizations of catalyst metal type and its morphology. Combining the respective advantages of Ag and Au in the MaCE as a Ag/Au bilayer configuration leads to quite stable etch reaction upon a prolonged etch duration up to >5 h. Further, the permeable nature of the optimized Ag/Au bilayer metal catalyst enables the etching of pattern features having very large lateral dimension. Problems such as the generation of micro/nanostructures and chemical attacks on the top of pattern surface are successfully overcome by process optimizations such as post‐partum sonication treatment and etchant formulation control. The method can also be successful to vertical micromachining of Si substrate having other crystal orientations than Si(100), such as Si(110) and Si(111). The simple, easy, and low‐cost nature of present approach may be a great help in bulk micromachining of Si for various applications such as microelectromechanical system (MEMS), micro total analysis system (μTAS), and so forth.     

Formation and mechanism of silicon nanostructures by Ni-assisted etching

Instead of noble metal like Pt, Au and Ag, cheap Ni nanoparticles (Ni NPs) were used to fabricate silicon nanostructures. Ni was found to be etched off during the etching process, while forming silicon nanostructures with very low reflectance of 1.59 % from 400 to 900 nm. The formation mechanism of silicon nanostructures by Ni-assisted etching was presented from the point of view of the low electronegativity of Ni. The Ni NPs were found being etched off during the assisted etching process, which implies that the transfer rate of electrons from Si to Ni is slower than that from Ni to O^? in the case of using Ni as assisted metal. The reason of sparser and deeper silicon nanostructures etched in lower H₂O₂ concentration solution is that the Ni NPs can be lasted for longer time in the etching solution with lower H₂O₂ concentration so that more silicon atoms will be oxidized and then removed for those under Ni NPs due to the hole transfer and those where uncovered by Ni NPs due to the hole diffusion.     

A facile method for fabrication of large area graphene nanostructures

In this study, we introduce a novel method to produce large area interconnected graphene nanostructures. A single layer CVD (Chemical Vapor Deposition) grown graphene was nanostructured by employing dewetted Ni thin film as an etching mask for the underlying graphene. As a result, a network of graphene nanostructures with irregular shapes and widths down to 10 nm is obtained. The FET (field effect transistor) devices fabricated employing the nanostructured graphene as channel material exhibit increased on/off current ratio compared to pristine graphene indicating a slight band gap opening due to the quantum confinement effect in such narrow graphene nanostructures. This technique can be useful for the large scale fabrication of graphene based electronic devices such as FETs and sensors.     

High density Si/ZnO core/shell nanowire arrays for photoelectrochemical water splitting

Si/ZnO core/shell nanowire (NW) arrays were fabricated using atomic layer deposition of ZnO shell on n-Si NW arrays prepared by metal assisted electroless etching method. Scanning electron microscopy, transmission electron microscopy and X-ray diffraction were utilized to characterize the core/shell structures. Water splitting performance of the core/shell structures was preliminarily studied. The Si/ZnO core/shell NW arrays yielded significantly higher photocurrent density than the planar Si/ZnO structure due to their low reflectance and high surface area. The photoelectrochemical efficiency was found to be 0.035 and 0.002 % for 10 μm-long Si/ZnO NW array and planar Si/ZnO sample, respectively. These results suggested that core/shell structure is superior to planar heterojunction for PEC electrode design. We demonstrated the dependence of photocurrent density on the length of the core/shell array, and analyzed the reasons why longer NW arrays could produce higher photocurrent density. The relationship between the thickness of ZnO shell and the photoconversion efficiency of Si/ZnO NW arrays was also discussed. By applying the core/shell structure in electrode design, one may be able to improve the photoelectrochemical efficiency and photovoltaic device performance.     

Antireflective hydrophobic si subwavelength structures using thermally dewetted Ni/SiO2 nanomask patterns

We report the disordered silicon (Si) subwavelength structures (SWSs), which are fabricated with the use of inductively coupled plasma (ICP) etching in SiCl4 gas using nickel/silicon dioxide (Ni/SiO2) nanopattens as the etch mask, on Si substrates by varying the etching parameters for broadband antireflective and self-cleaning surfaces. For the fabricated Si SWSs, the antireflection characteristics are experimentally investigated and a theoretical analysis is made based on the rigorous coupled-wave analysis method. The desirable dot-like Ni nanoparticles on SiO2/Si substrates are formed by the thermal dewetting process of Ni films at 900 degrees C. The truncated cone shaped Si SWS with a high average height of 790 +/- 23 nm, which is fabricated by ICP etching with 5 sccm SiCl4 at 50 W RF power with additional 200 W ICP power under 10 mTorr process pressure, exhibits a low average reflectance of approximately 5% over a wide wavelength range of 450-1050 nm. The water contact angle of 110 degrees is obtained, indicating a hydrophobic surface. The calculated reflectance results are also reasonably consistent with the experimental data.     

ZnO/CdS/Ag复合光催化剂的制备及其催化和抗菌性能

先用水热反应合成六方晶相CdS多层级花状微球并在其表面生长ZnO纳米棒形成均匀的ZnO/CdS复合结构,然后用光还原法将Ag纳米颗粒负载于ZnO纳米棒制备出ZnO/CdS/Ag三元半导体光催化剂,对其进行扫描电镜和透射电镜观察、光电性能测试、活性基团捕获实验以及光催化降解和抗菌性能测试,研究其对亚甲基蓝(MB)的降解和抗菌性能。结果表明：ZnO纳米棒均匀生长在CdS微球表面,CdS晶体没有明显裸露,Ag纳米粒子负载在ZnO纳米棒的表面;ZnO/CdS/Ag三元复合光催化剂有良好的可见光响应、较低的阻抗和较高的光电流密度;ZnO/CdS/Ag复合光催化剂能同时产生羟基和超氧自由基等活性氧基团;ZnO/CdS/Ag三元复合光催化剂对亚甲基蓝(MB)的30 min降解率高于90%;0.25 mg/mL的ZnO/CdS/Ag对革兰氏阴性菌(大肠杆菌)的灭菌率高于96%,对革兰氏阳性菌(金黄色葡萄球菌)能完全灭除。     

Plasma‐Induced Hetero‐Nanostructures on a Polymer with Selective Metal Co‐Deposition

Plasma‐induced pattern formation is explored on polyethylene terephthalate (PET) using an oxygen plasma glow discharge. The nanostructures on PET are formed through preferential etching directed by the co‐deposition of metallic elements, such as Cr or Fe, sputtered from a stainless‐steel cathode. The local islands formed by metal co‐deposition have significantly slower etching rates than those of the pristine regions on PET, generating anisotropic nanostructures in pillar‐ or hair‐like form during plasma etching. By covering the cathode with the appropriate material, the desired metallic or polymeric elements can be co‐deposited onto the target surfaces. When the cathode is covered by a relatively soft material composed of only carbon and hydrogen, such as polystyrene, nanostructures typically induced by preferential etching are not observed on the PET surface, and the surfaces are uniformly etched. A variety of metals, such as Ag, Cu, Pt, or Si, can be successfully co‐deposited onto the PET surfaces by simply using a cathode covered in the desired metal; high‐aspect‐ratio nanostructures coated with the co‐deposited metal are subsequently formed. Therefore this simple single‐step method for forming hetero‐nanostructures—that is, nanoscale hair‐like polymer structures decorated with metals—can be used to produce nanostructures for various applications, such as catalysts, sensors, or energy devices.